CN108439476B - Preparation of low-valence manganese oxide, product and synthetic lithium ion sieve precursor L i1.6Mn1.6O4Application of - Google Patents

Preparation of low-valence manganese oxide, product and synthetic lithium ion sieve precursor L i1.6Mn1.6O4Application of Download PDF

Info

Publication number
CN108439476B
CN108439476B CN201810368209.1A CN201810368209A CN108439476B CN 108439476 B CN108439476 B CN 108439476B CN 201810368209 A CN201810368209 A CN 201810368209A CN 108439476 B CN108439476 B CN 108439476B
Authority
CN
China
Prior art keywords
manganese
low
mixture
valence
manganese oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810368209.1A
Other languages
Chinese (zh)
Other versions
CN108439476A (en
Inventor
王磊
孟晓荣
吴浩
黄丹曦
陈立成
李陈
陈铖
霍姗姗
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xi'an jinzang membrane Environmental Protection Technology Co.,Ltd.
Original Assignee
Shaanxi Membrane Separation Technology Research Institute Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi Membrane Separation Technology Research Institute Co ltd filed Critical Shaanxi Membrane Separation Technology Research Institute Co ltd
Priority to CN201810368209.1A priority Critical patent/CN108439476B/en
Publication of CN108439476A publication Critical patent/CN108439476A/en
Application granted granted Critical
Publication of CN108439476B publication Critical patent/CN108439476B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
    • C01G45/1214—Permanganates ([MnO]4-) or manganates ([MnO4]2-) containing alkali metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a preparation method of low-valence manganese oxide, a product and synthesis L i1.6Mn1.6O4The use of (1), the preparation of the low-valent manganese oxide comprises: mixing manganese dioxide with a liquid-phase organic reducing agent, and preparing the mixture by a chemical reduction method; the low valence manganese-oxygen mixture comprises a mixture of manganous-manganic oxide, manganous oxide, manganese oxyhydroxide and part of unreduced manganese dioxide, and the average valence of manganese elements of the mixture is between 3.01 and 3.55. The invention reduces the manganese dioxide into a mixture of low-valence manganese oxide compounds by using an active liquid-phase organic micromolecular reducing agent to react with the manganese dioxide raw material under hydrothermal conditions. Compared with the traditional method, the process does not need high-temperature roasting, and is a clean production process with mild conditions, high efficiency and low energy consumption. Has the characteristics of energy conservation and low cost.

Description

Preparation of low-valence manganese oxide, product and synthetic lithium ion sieve precursor L i1.6Mn1.6O4Application of
Technical Field
The invention belongs to the field of energy-saving production of inorganic compounds, and particularly relates to preparation and product of low-valence manganese oxide and synthesized lithium ion sieve precursor L i1.6Mn1.6O4The use of (1).
Background
MnO2The compound is an oxidant with mild property, can oxidize active alcohol hydroxyl into aldehyde or ketone under neutral or alkaline condition, wherein the allyl and benzyl alcohol are most active, and can react at room temperature under the neutral condition to be oxidized into aldehyde. However, during the production and storage of industrial manganese dioxide, the surface of manganese dioxide powder is deactivated and oxygen is lostChemical capacity, resulting in the difficult efficient redox reaction of manganese dioxide with alcohol, and lithium manganese oxide lithium ion sieve precursor L i1+xMn2-xO4In the synthesis, the valence state of manganese is 3-4, and the synthesis of the ion sieve usually requires the use of a low-valence oxide of manganese, such as trivalent manganese oxide Mn2O3Manganese oxyhydroxide MnO (OH), manganomanganic oxide Mn3O4And the like.
In the methods provided in most patents, manganese oxide and manganese dioxide are obtained by high temperature roasting of manganese dioxide for decomposition. In the preparation method of the CN107138126A lithium ion sieve adsorbent and the method for adsorbing lithium ions, step 1, weighing a manganese-containing compound and a lithium-containing compound in a mass ratio of 6: 1-14: 1, uniformly mixing in a crucible, roasting in a muffle furnace at 400-1000 ℃ for 60-300 min, cooling to room temperature, and grinding to obtain a lithium type ion sieve; the manganese-containing compound is manganese dioxide, so that the high-temperature reaction has high energy consumption, pollutes the environment and is not environment-friendly;
for example, "CN 101264935A A method for reducing MnO in anode mud by high-temp2The method for reducing MnO comprises the following steps: uniformly mixing electrolytic manganese anode mud and a reducing agent in a reaction device, reacting for 1-6 h at 800-1600 ℃, naturally cooling to room temperature under the protection of nitrogen and reducing atmosphere to obtain a mixed product containing MnO particles, and directly returning the product to electrolytic manganese metal production to be used as a raw material or further separating and purifying to obtain an MnO product.
For another example: patent "CN 103121724B A method for preparing lithium ion sieve MnO2·0.5H2O and its precursor L i1.6Mn1.6O4The method gives a precursor L i which is obtained by taking inorganic manganese salt and lithium salt as raw materials, carrying out one-step hydrothermal synthesis on an intermediate, and then roasting at a low temperature1.6Mn1.6O4Then, the precursor is subjected to acid treatment to extract L i in the precursor to form an H-type ion sieve, and the H-type ion sieve is washed, filtered and dried to obtain the ion sieve adsorbent MnO with the lithium ion sieving effect2·0.5H2O, i.e. reaction of potassium permanganate with manganous saltPreparation L i1.6Mn1.6O4And the amount of waste water generated in the reaction process is large, which is not beneficial to the environmental protection in the later period.
It can be seen that in the patents relating to the preparation of lithium manganese oxide lithium ion sieves from manganese dioxide, the required low valence manganese oxide is prepared by high temperature decomposition or by reacting a divalent manganese salt with a large amount of an inorganic oxidant such as potassium permanganate to obtain an intermediate valence manganese oxide compound. High energy consumption, large amount of waste water and high production cost.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior preparation technology, the invention aims to provide a preparation method of low-valence manganese oxide, a product and a synthetic lithium ion sieve precursor L i1.6Mn1.6O4The process does not need high-temperature roasting, and is a clean production process with mild conditions, high efficiency and low energy consumption.
In order to achieve the purpose, the invention adopts the following technical scheme:
a low-valent manganese oxide, the preparation of which comprises: mixing manganese dioxide with a liquid-phase organic reducing agent, and preparing the mixture by a chemical reduction method;
the low-valence manganese oxide comprises a mixture of trimanganese tetroxide, manganic oxide, manganese oxyhydroxide and manganese dioxide, and the average valence state of the manganese element of the low-valence manganese oxide is 3.01-3.55.
The preparation method of low-valence manganese oxide comprises the steps of mixing manganese dioxide with a liquid-phase organic reducing agent, and preparing the mixture by a chemical reduction method;
the amount of the liquid-phase organic reducing agent is 1-3 times of that of the manganese dioxide raw material.
Optionally, the liquid-phase organic reducing agent is one or more of primary alcohol, allyl alcohol and benzyl alcohol containing active hydroxyl groups.
Optionally, mixing manganese dioxide and a liquid-phase organic reducing agent, placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal reaction for 12-24 h at 120-140 ℃, cooling along with a furnace, filtering to remove residual liquid organic mixture and water, and drying the solid to obtain the low-valence manganese-oxygen mixture.
The low-valence manganese oxide is prepared by the preparation method of the low-valence manganese oxide.
Low-valence manganese oxide or low-valence manganese oxide prepared by the preparation method of low-valence manganese oxide is used for preparing manganese ferrite lithium ion sieve precursor L i1.6Mn1.6O4The use of (1).
Compared with the prior art, the invention has the beneficial effects that:
the method reduces the manganese dioxide into a mixture of low-valence manganese oxide compounds by using an active liquid-phase organic micromolecule reducing agent to react with the manganese dioxide raw material under mild heterogeneous conditions. Compared with the traditional method for obtaining manganese sesquioxide by decomposing manganese dioxide at high temperature of 1100 DEG C
In comparison, the process does not need high-temperature roasting, and is a clean production process with mild conditions, high efficiency and low energy consumption. Has the characteristics of energy conservation and low cost.
Detailed Description
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Example 1:
(1) accurately weighing 50gMnO2(analytically pure, Komeo) sample, determining the manganese content to be 95.20% by EDTA titration method, adding 200m L absolute ethyl alcohol, magnetically stirring the mixture in a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene lining kettle until the mixture is uniform, adding a stainless steel outer sleeve for sealing, placing the mixture in a 120 ℃ oven for heating reaction for 24 hours, taking out the mixture and cooling the mixture to room temperature, and drying the obtained viscous liquid mixture at the normal pressure of 80 ℃ for 6 hours to obtain 49.80 g of low-valence manganese oxide mixture.
(2) Accurately weighing 0.5g of the mixture obtained in the step (1), mixing and heating the mixture by using a proper amount of 1/1 hydrochloric acid and a small amount of water until the sample is completely dissolved and residual Cl in a yellow-green solution is formed2Drive off and transfer the solution to a 250m L capacityDiluting to a scale mark in a bottle, shaking up, transferring 25.00m L by using a pipette, adding 10m L of ammonia/ammonium chloride buffer solution with the pH value of 10 and 0.15g of hydroxylamine hydrochloride, stirring and dissolving, adding 5 drops of K-B indicator, dropping EDTA standard solution with known accurate concentration until the solution is pure blue, carrying out 3 experiments in parallel, and calculating the content of Mn in the sample to be 95.20% according to the formula (1).
Figure GDA0001680285710000041
(3) Accurately weighing 0.1005g of the mixture of low valence manganese oxides of (1) in a 250m L conical flask, adding Na with known accurate concentration2C2O4The standard solution 25.00m L was diluted with 15m L deionized water and shaken well, then 10m L of 3 mol/L sulfuric acid was added, placed on a water bath at 80 ℃ and heated until the sample was completely dissolved, and KMnO of known precise concentration was used while hot4Back titration of unreacted Na from standard solution2C2O4The average valence of manganese in the low-valence manganese oxide is 3.01 by the following formula (2) through 3 parallel experiments.
Figure GDA0001680285710000051
(4) Mixing the manganese oxide with lithium-containing inorganic powder (lithium hydroxide) according to the lithium-manganese ratio of 1/1, and preparing a lithium manganese oxide lithium ion sieve precursor L i by a high-temperature solid phase method (refer to the preparation method of CN107138126A lithium ion sieve adsorbent and the method of absorbing lithium ions)'1.6Mn1.6O4After low-acid delithiation, the solution was adsorbed for 10 hours in an aqueous environment containing 0.2 g/L of lithium ions at pH 10 to reach equilibrium, and the amount of adsorbed lithium was found to be 25.3 mg/g.
Example 2:
(1) accurately weighing 50gMnO2(analytically pure, Komeo) sample, adding 200m L allyl alcohol, magnetically stirring in a polytetrafluoroethylene lined kettle of a high-pressure hydrothermal reaction kettle until uniform, sealing with a stainless steel jacket, heating in a 120 ℃ oven for reaction for 24h, taking out, and cooling to room temperatureAfter the temperature is raised, the obtained viscous liquid mixture is dried for 12 hours at the normal pressure of 60 ℃ to obtain 49.70g of a mixture of low-valence manganese oxides.
(2) The content of manganese in the product was measured in the same manner as in (2) in example 1, and the content of Mn in the mixture was measured to be 95.24%.
(3) The valence of manganese in the product was determined in the same manner as in (3) in example 1, and the average valence of manganese in the lower manganese oxide was found to be 3.05.
(4) Lithium manganese oxide lithium ion sieve precursor L i prepared and obtained by using product and lithium-containing inorganic powder1.6Mn1.6O4The preparation method was the same as that of (4) in example 1, and after equilibrium was reached by adsorption for 8 hours, the amount of adsorbed lithium was 21.4 mg/g.
Example 3:
(1) accurately weighing 50gMnO2(analytically pure, Komeo) sample is added with 100m L absolute ethyl alcohol, the mixture is magnetically stirred in a polytetrafluoroethylene lining kettle of a high-pressure hydrothermal reaction kettle until the mixture is uniform, a stainless steel outer sleeve is added for sealing, the mixture is placed in a 120 ℃ oven for heating reaction for 24 hours, the mixture is taken out and cooled to room temperature, and the obtained viscous liquid mixture is dried for 6 hours at the normal pressure of 80 ℃ to obtain 49.60g of low-valence manganese oxide mixture.
(2) The content of manganese in the product was measured in the same manner as in (2) in example 1, and the content of Mn in the mixture was measured to be 95.22%.
(3) The valence of manganese in the product was determined in the same manner as in (3) in example 1, and the average valence of manganese in the lower manganese oxide was found to be 3.55.
(4) Lithium manganese oxide lithium ion sieve precursor L i prepared and obtained by using product and lithium-containing inorganic powder1.6Mn1.6O4The preparation method was the same as that of (4) in example 1, and after equilibrium was reached by adsorption for 8 hours, the amount of adsorbed lithium was 21.2 mg/g.
Example 4:
(1) accurately weighing 50gMnO2(analytically pure, Koimeu) sample, adding 300m L benzyl alcohol, magnetically stirring in a polytetrafluoroethylene lined kettle of a high-pressure hydrothermal reaction kettle until the mixture is uniform, and sealing with a stainless steel outer sleeveThe mixture is put in a baking oven with the temperature of 140 ℃ for heating reaction for 28 hours, and after the temperature of the mixture is reduced along with the furnace, the obtained viscous liquid mixture is dried for 6 hours at the temperature of 80 ℃ under normal pressure, and 49.56g of mixture of low-valence manganese oxide is obtained.
(2) The content of manganese in the product was measured in the same manner as in (2) in example 1, and the content of Mn in the mixture was measured to be 95.34%.
(3) The valence of manganese in the product was determined in the same manner as in (3) in example 1, and the average valence of manganese in the lower manganese oxide was found to be 3.01.
(4) Lithium manganese oxide lithium ion sieve precursor L i prepared and obtained by using product and lithium-containing inorganic powder1.6Mn1.6O4The preparation method was the same as that of example 1, and the amount of adsorbed lithium was 25.12mg/g, as measured after 6 hours.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (1)

1. Low-valence manganese oxide used for preparing manganese oxide lithium ion sieve precursor L i1.6Mn1.6O4Characterized in that the preparation of the low-valent manganese oxide comprises: mixing manganese dioxide with a liquid-phase organic reducing agent, and preparing the mixture by a chemical reduction method;
the organic reducing agent is benzyl alcohol, the adding amount of manganese dioxide is 50g, and the adding amount of the benzyl alcohol is 300m L;
mixing manganese dioxide and a liquid-phase organic reducing agent, placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal reaction for 28h at 140 ℃, cooling along with a furnace, filtering to remove residual liquid organic mixture and water, and drying the obtained viscous liquid mixture for 6h at the normal pressure of 80 ℃ to obtain a low-valence manganese-oxygen mixture;
the average valence of the manganese element of the low valence manganese-oxygen mixture is 3.01.
CN201810368209.1A 2018-04-23 2018-04-23 Preparation of low-valence manganese oxide, product and synthetic lithium ion sieve precursor L i1.6Mn1.6O4Application of Active CN108439476B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810368209.1A CN108439476B (en) 2018-04-23 2018-04-23 Preparation of low-valence manganese oxide, product and synthetic lithium ion sieve precursor L i1.6Mn1.6O4Application of

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810368209.1A CN108439476B (en) 2018-04-23 2018-04-23 Preparation of low-valence manganese oxide, product and synthetic lithium ion sieve precursor L i1.6Mn1.6O4Application of

Publications (2)

Publication Number Publication Date
CN108439476A CN108439476A (en) 2018-08-24
CN108439476B true CN108439476B (en) 2020-07-28

Family

ID=63200711

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810368209.1A Active CN108439476B (en) 2018-04-23 2018-04-23 Preparation of low-valence manganese oxide, product and synthetic lithium ion sieve precursor L i1.6Mn1.6O4Application of

Country Status (1)

Country Link
CN (1) CN108439476B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109289757B (en) * 2018-12-07 2021-03-16 中国科学院青海盐湖研究所 Hexagonal dendritic manganese lithium ion sieve adsorbent and preparation method thereof
CN109289758B (en) * 2018-12-07 2021-04-02 中国科学院青海盐湖研究所 Hexagonal flaky manganese lithium ion sieve adsorbent and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59223236A (en) * 1983-06-02 1984-12-15 Chuo Denki Kogyo Kk Production of high purity manganese compound
CN106745285A (en) * 2017-03-01 2017-05-31 哈尔滨工业大学 A kind of α MnO2The preparation method of nano wire
CN107138126A (en) * 2017-07-18 2017-09-08 河北工程大学 A kind of preparation method of lithium ion sieve adsorbant and the method for adsorbing lithium ion

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59223236A (en) * 1983-06-02 1984-12-15 Chuo Denki Kogyo Kk Production of high purity manganese compound
CN106745285A (en) * 2017-03-01 2017-05-31 哈尔滨工业大学 A kind of α MnO2The preparation method of nano wire
CN107138126A (en) * 2017-07-18 2017-09-08 河北工程大学 A kind of preparation method of lithium ion sieve adsorbant and the method for adsorbing lithium ion

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Low temperature preparation of nanocrystalline Mn2O3 via ethanol-thermal reduction of MnO2;wenliang He et al.;《Journal of Crystal Growth》;20031231;285-288 *

Also Published As

Publication number Publication date
CN108439476A (en) 2018-08-24

Similar Documents

Publication Publication Date Title
Feng et al. Alkali metal ions insertion/extraction reactions with hollandite-type manganese oxide in the aqueous phase
CN101961634B (en) Manganese series lithium ion sieve adsorbent and preparation method of precursor thereof
CN103991908B (en) By the method for cation doping regulation and control lithium ion sieve stability
CN1097558C (en) Preparation of lithium manganese oxide spinel
CN112670473B (en) Ternary precursor, preparation method thereof, lithium ion battery positive electrode material and lithium ion battery
CN101928042A (en) Spinel-type lithium-ion sieve and method for preparing precursor LiMn2O4 thereof
CN108439476B (en) Preparation of low-valence manganese oxide, product and synthetic lithium ion sieve precursor L i1.6Mn1.6O4Application of
Feng et al. Li+ extraction/insertion reactions with LiZn0. 5Mn1. 5O4 spinel in the aqueous phase
JP2024502688A (en) Coated lithium ion sieve and its manufacturing method
CN103272554A (en) Method for preparing lithium manganese oxide-type lithium adsorbent
CN101224907A (en) Method for preparing nano lanthanum-strontium-manganese oxide
CN104941569A (en) Method for preparing manganese-based lithium-ion sieve adsorbent
CN101898797A (en) High-purity trimanganese tetroxide and preparation method thereof
CN114225895A (en) La-Fe-Al composite metal oxide, preparation method and application
JPH11240721A (en) New production of spinel type lithium manganese compound oxide and positive electrode active substance for secondary battery
EP0842120B1 (en) An improved process for making a lithiated lithium manganese oxide spinel
CN110498420A (en) A method of preparing a series of high stability amorphous bimetallic silicates
CN108554366B (en) Method for preparing manganese oxide ion sieve precursor LixMn3-xO4 by one-step method
CN106587120A (en) Water treatment agent based on laminated composite metal hydroxide and preparation method of water treatment agent
CN102633306A (en) High-purity trimanganese tetroxide and preparation method of same
CN108585052B (en) Method for synthesizing manganese ferrite lithium ion sieve precursor Li by heterogeneous reduction of manganese dioxide1.6Mn1.6O4Method (2)
CN108585049B (en) Manganous-manganic oxide and preparation method thereof
CN106517345B (en) Method for preparing ultrafine manganese dioxide by using potassium permanganate and potassium manganate
JP4019070B2 (en) Positive electrode active material for lithium primary battery
JP3742646B1 (en) Cathode active material for lithium batteries

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20211215

Address after: 710068 Room 301, Shaanxi Membrane Separation Technology Research Institute, No. 13, middle section of Yanta Road, Beilin District, Xi'an City, Shaanxi Province

Patentee after: Xi'an jinzang membrane Environmental Protection Technology Co.,Ltd.

Address before: Room S205, innovation building, No.25, Gaoxin 1st Road, high tech Zone, Xi'an, Shaanxi 710068

Patentee before: SHAANXI MEMBRANE SEPARATION TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd.

TR01 Transfer of patent right